61, NUMBER 9
29 AUGUST 1988
Dipartimento
di Fisica, Universita
and
Giuseppe Vitiello
Dipartimento di Fisica, Universita di Salerno, Salerno, Italy, and
Sezione di Napoli, Istituto Nazionale di Fisica Nucleare, Napoli, Italy
(Received 23 May 1988)
We show that the usually neglected interaction between the electric dipole of the water molecule and
the quantized electromagnetic radiation field can be treated in the context of a recent quantum field
theoretical formulation of collective dynamics. We find the emergence of collective modes and the appearance of permanent electric polarization around any electrically polarized impurity.
PACS nUmbers:
'
radiation gauge):
jv
H= QHJ,
H,
2I
LJ2+A d, ),
(2)
I =2
dm2
(dg
=0.82 A)
(3)
(4)
1085
VOLUME
61, NUMBER 9
that describes the dynamics of our system (we use the natural units h
Z=
[dydee
29 AUGUST 1988
=c =1),
]),
(5)
where the action integral (u is the unit vector in the dipole direction) is given by
4n r, (.
at
(u,' t)
y*(u, t)
'
+,
2ed,
i'
V' ig
rk
1/2
4m'~
y(u, t)
(7)
L2
sin8
and
tion
a8
a+a'
sin8
a0
dn(*(u,t)g(u, t) = l.
6LdQdt =0,
(io)
4md2,
i2ed,'
g(u,' t)
ab, (k, t)
N
k
g(e, u)
V
2ed, e(k)
((u, t) =g(
C(
(t)Yf"(u),
(t) denotes the number of molecules that populate the rotational state tl, m) of our rigid rotator,
which, neglecting all interactions, at thermal equilibrium
should follow a Boltzmann distribution
with F(=l(l
+ I )/ 4md~. Under normal conditions (unpolarized bulk
water) the levels l =0 and l = 1 have comparable populaN C(
t
1086
equations:
b, (k, t)e'"']g
(u, t),
(i4)
(13)
t)
(12)
t),
Lagrangian
(9)
&(u, t) =N'q(u,
b the
a, (k, t) is the amplitude of the mode k with polarizar [k e, (k) 0, from the transversality condition].
(is)
"
yo(t) =Coo(t),
(i7)
.
61, NUMBER 9
VOLUME
where
0= 4ed,
Q3
2copV
G~o.
(18)
Note that in pure water (H20), G=-17. Taking advantage of the rotational symmetry of the problem, our system can be further simplified by setting y (t ) = yi (t )
and b (t) =b(t). One thus obtains
yp(t
) = 3 n b (t ) yl (t ),
= nb(t
yl(t)
yp
'+ 3
y|
=cos
yp(0)
yl(0)
I'=-,
'
yp,
specifies
the initial
co
(22)
sin'Op,
pp,
pp- y=x/2,
(23)
rp(t) =rp
d, j
(28)
(29)
Ed,
I0, 0) and
with eigenvalues
(I /$3)[1 +cos2O+( 1
sin22O)
I/2] I/2
(24)
'/',
j3 ) [sin2a (I ) I
(25)
1
~p,
=(cop/2) [1 T-
(31)
(32)
]/2Vd.
For Vd not too strong (a & n/8) the dynamics of our system is practically unchanged, except for the rotation
(30), induced by the electrostatic mixing, which modifies
the form (28) of the polarization P3 as
(1+4'/co/)'/1,
and
tga
and
P3 (t ) = (1/
cop) t.
Vd=
yi, b, respectively,
pp
(27)
P, =(gln ulg)
= (2/ J3)rp(t )r, (t ) cos(co2
cycle:
p =pl
=(2COS2Op) '/2n.
0,
Op,
Ib(0)l' =0
If we call I p, I 1, 8 and
of
r,
(21)
Op(0(Op~ x/2)
(26)
of motion:
Op
n.
sin 2Op]
' =I,
+ lbl = 3n
=242[1
col
(19)
) yp(t),
29 AUGUST 1988
j) '
] t )j.
(33)
r,'),
(34)
1 attains very
in the region where 2'/cop is
respectable values. Note that in the absence of the collective interaction analyzed in this paper, one must have
ro -r&', as prescribed by thermal equilibrium, and no
significant electric polarization can emerge even for rath-
which
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VoLUME61, NUMBER 9
1088
29 AUGUs~ 1988
We wish to express our thanks to Professor Silvia Doglia for her encouragement and for giving us useful information on the present experimental knowledge of wa-
ter.